We investigated the origin of magnetic behaviors induced by an asymmetric spin exchange interaction in Fe-site engineered lead iron niobate [Pb(Fe_1/2Nb_1/2)O₃, PFN], which exhibits a room-temperature multiferroicity. The magnitude of spin exchange interaction was regulated by the introduced transition metals with a distinct Bohr magneton, i.e., Cr, Co, and Ni. All compositions were found to have a single-phase perovskite structure keeping their ferroelectric order except for Cr introduction. We discovered that the incorporation of each transition metal imposes a distinct magnetic behavior on the lead iron niobate system; antiferro-, hard ferro-, and soft ferromagnetism for Cr, Co, and Ni, respectively. This indicates that orbital occupancy and interatomic distance play key roles in the determination of magnetic behavior rather than the magnitude of the individual Bohr magneton. Further investigations are planned, such as X-ray absorption spectroscopy, to clarify the origin of magnetic properties in this system.

Multiferroics exhibiting the coexistence and a possible coupling of ferromagnetic and ferroelectric order are attracting widespread interest in terms of academic interests and possible applications. However, room-temperature single-phase multiferroics with soft ferromagnetic and displacive ferroelectric properties are still rare owing to the contradiction in the origin of ferromagnetism and ferroelectricity. In this study, we demonstrated that sizable ferromagnetic properties are induced in the ferroelectric bismuth ferrite-barium titanate system simply by introducing Co ions into the A-site. It is noted that all modified compositions exhibit well-saturated magnetic hysteresis loops at room temperature. Especially, 70Bi_0.95Co_0.05FeO₃-30Ba_0.95Co_0.05TiO₃ manifests noticeable ferroelectric and ferromagnetic properties; the spontaneous polarization and the saturation magnetization are 42 μC/㎠ and 3.6 emu/g, respectively. We expect that our methodology will be widely used in the development of perovskite-structured multiferroic oxides.